EP0093502B2 - Ammonia production process - Google Patents

Ammonia production process Download PDF

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Publication number
EP0093502B2
EP0093502B2 EP83301801A EP83301801A EP0093502B2 EP 0093502 B2 EP0093502 B2 EP 0093502B2 EP 83301801 A EP83301801 A EP 83301801A EP 83301801 A EP83301801 A EP 83301801A EP 0093502 B2 EP0093502 B2 EP 0093502B2
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Prior art keywords
gas
hydrogen
ammonia
nitrogen
synthesis
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German (de)
English (en)
French (fr)
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EP0093502A1 (en
EP0093502B1 (en
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Alwyn Pinto
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0482—Process control; Start-up or cooling-down procedures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0476—Purge gas treatment, e.g. for removal of inert gases or recovery of H2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to an ammonia production process, in particular to such a process capable of operation at a relatively low rate of energy consumption per unit quantity of product.
  • a typical ammonia production process comprises
  • X controlling the rate of flow of the steam enriched in hydrogen so that the hydrogen to nitrogen molar ratio of the gas entering the synthesis catalyst is in the range 1.0to 2.5; and Y. operating step (a) in at least one adiabatic catalyst bed and providing the endothermic heat of reaction by preheating, whereby the temperature of the reacting gas falls as it proceeds through the catalyst bed.
  • an ammonia production process may comprise steps (a) to (f) above and can be characterised by using in step (b) air enriched with oxygen up to an oxygen content not over 50% v/v.
  • the oxygen enrichment is moderate and, except in a process involving carbon oxides removal as methanol, does not introduce less than 1 molecule of nitrogen per 3 molecules of hydrogen.
  • it introduces an exess of nitrogen, such that after steps (c) and (d) there are 2.0 to 2.9, especially 2.2 to 2.8, molecules of hydrogen per molecule of nitrogen.
  • the oxygen content of the enriched air is preferably over 25% v/v for example in the range 30-45, especially 30-40% v/v.
  • a mixture is conveniently the by-product stream for a process designed primarily to produce pure nitrogen.
  • One such process comprises compressing air, cooling it, fractionating it in a single stage to give nitrogen overhead and an oxygen enriched mixture as bottoms and expanding the nitrogen and the mixture to cool the inlet compressed air.
  • the working pressure of such a process is typically in the range 5-10 bar abs.
  • the nitrogen can be recovered as liquid or gas and can be used in the ammonia production process in ways described below.
  • the oxygen-containing mixtures can be delivered at the working pressure or less, but usually will require compression since secondary reforming is carried out preferably at a pressure higher than that used for the air separation. Suitable processes are described in Kirk-Othmer's Encyclopedia of Chemical Technology, 3rd Edition, vol. 15, pages 935-936 and in «High purity nitrogen plants», leaflet PD 38/6, 78a issued by Petro- carbon
  • Another such process is a selective adsorption system.
  • This can use a zeolite, by which nitrogen is preferentially adsorbed from air, or a carbon adsorbent, by which oxygen is adsorbed more rapidly than nitrogen, a nitrogen stream is passed out and an oxygen-enriched mixture (typically 35% 0 2 , 65% N 2 ) is obtained by desorption.
  • an oxygen-enriched mixture typically 35% 0 2 , 65% N 2
  • the nitrogen product is preferably stored, for injection into the ammonia production plant in start-up, stand-by or shut down phases, in particular for purposes such as a catalyst heating medium during start-up, a flushing or circulating gas during periods of interrupted production when the plant is to be kept hot and ready for rapidly restarting production, a blanketing gas during catalyst shut down or waiting periods and a dilution gas during catalyst activation by reduction.
  • nitrogen and enriched-air production step with a process involving steps (a) to (f) is thus a technological unity.
  • nitrogen storage facilities are filled, nitrogen can be vented to atmosphere, possibly with cold recovery in the ammonia recovery section of the production process and/or with changed operation of air separation so as to deliver oxygen-enriched air at increased pressure.
  • step (b) includes selective oxidation of carbon monoxide, this can use the enriched air and then involves a smaller introduction of nitrogen than when air is used as the oxidant.
  • step (a) is carried out by preheating the reactants and then allowing them to react in one or more adiabatic catalyst beds.
  • rapid start-up or shut down would be possible using the process of our European application 49967 or the Fluor process (US 3 743 488, 3 795 485), but has been thought uneconomic in the absence of an on-site nitrogen supply.
  • the air separation plant can be operated without the other steps in ammonia production, for example during start-up or during a waiting period after stored nitrogen has been used up, to provide the required nitrogen. In such events the oxygen-enriched air is stored or disposed of.
  • the pressure at which steps (a) to (d) are operated is preferably at least 10 bar abs. and especially at least 30 bar abs. to make most advantageous use of the oxygen-enriched air.
  • the upper limit is likely to be 120, conveniently 80 bar abs.
  • Such pressures apply to the outlet of step (a), and the pressures at subsequent steps are lower as the result of resistance to gas flow in reactors and pipes.
  • the gas is compressed if its pressure is not high enough for ammonia synthesis.
  • the extent of such compression is preferably not more than by 20-80 bar, and can be by as little as 25% or less such as occurs in a synthesis gas circulating pump. When compression is by such a preferred limited extent, it is preferred to remove excess nitrogen from synthesis gas after ammonia synthesis.
  • the power for the compressors in the air separation plant, for secondary reformer air feed and for synthesis gas, and for various pumps and other machinery, is conveniently derived from engines driven by steam produced in heat recovery from hot gases in the process. If desired such power drives can be partly or wholly electrical.
  • Step (a) is carried out at an outlet temperature under 800°C, preferably much lower, for example in the range 450-650°C.
  • step (a) is carried out by preheating followed by adiabatic reaction, in mode I or II mentioned above.
  • a catalyst having adequate low temperature activity should be used, such as a co-precipitated ni- ckel/alumina «CRG» catalyst or a catalyst comprising an active metal on an oxidic secondary support on a metal or alloy or highly calcined ceramic primary support as described in European published applications 21 736 or 45126 respectively.
  • step (a) can be in the range 40-80% v/v on a dry basis: in effect step (a) is acting thus as a «chemical preheater» for the reactants of step (b).
  • the steam to carbon molar ratio in step (a) is typically in the range 2.5 to 8.0, the higher ratios being used at higher pressures in the specific range.
  • the preheater for the primary reforming step or steps is preferably a pressurised furnace.
  • the pressure of the gases brought into heat exchange with the reactants is suitably at least 5 bar abs and preferably within 30 bar abs of the pressure of the reactants.
  • the life of the tubes through which the reactants flow in the furnace can be very usefully lengthened and/or the tubes can be made of thinner or cheaper metal.
  • the heating fluid is combustion gas a useful energy recovery as expansion engine power and waste heat is possible.
  • the heating fluid can be at a pressure dictated by its source, for example it may be helium heated in a nuclear reactor. If desired it can be combustion gas from a solid fuel, especially if combusted in a fluidised bed. Conveniently it is secondary reformer outlet gas.
  • the heating fluid after leaving the heat exchange surfaces is passed in heat exchange with one or more fluids such as saturated steam, process air, boiling water, boilder feed water, hydrocarbon feed or combustion air, in decreasing order of grade of heat recovery.
  • one or more fluids such as saturated steam, process air, boiling water, boilder feed water, hydrocarbon feed or combustion air, in decreasing order of grade of heat recovery.
  • Step (b) is normally carried out in an adiabatic reactor over a refractory-supported Ni or Co catalyst.
  • the primary reformer gas fed to it can be further preheated or can contain added steam or hydrocarbon.
  • the oxygen enriched air is fed at a temperature preferably in the range 400-800°C preferably at least partly as the result of using a compressor with limited, if any, cooling.
  • the outlet temperature of step (b) is preferably in the range 800-950°C.
  • the outlet methane content is preferably in the range 0.2 to 1.0% on a dry basis but can be greater, for example up to 3.0%, if it is desired not to introduce too much nitrogen and if provision is made to utilise the fuel value of the methane in the non-reactive gas discarded in step (f), as in the process of the second aspect of the invention described below or in our co-pending European application 49 967.
  • the gas leaving step (b) can if desired be used as the source of heat for step (a). Very usefully it can be cooled with recovery of heat in ways similar to those applied to preheater heating fluid, except that heat exchange with air is usually avoided for reasons of safety, and that cooling is not below carbon monoxide shift conversion inlet temperature. In conventional processing this temperature is in the range 300-400°C, especially 320-350°C, for «high temperature shift», usually over an iron-chrome catalyst.
  • the outlet temperature is typically in the range 400-450°C, whereafter the gas is cooled with heat recovery as above to 200-240°C and passes to low temperature shift over a copper-containing catalyst at an outlet temperature in the range 240-270°C.
  • the final CO content is up to 0.5% v/v on a dry basis, and can be followed by methanation.
  • the secondary reformer gas can be cooled to 250-325°C, with appropriately greater recovery of heat, and passed to shift at an outlet temperature up to 400°C, especially up to 350°C.
  • the catalyst can be supported cooper, suitably with zinc oxide and one or more refractory oxides such as alumina.
  • the selective oxidation catalyst is suitably supported platinum (0.01 to 2.0% w/w) containing possibly one or more of manganese, iron, cobalt or nickel as a promoter.
  • the gas now contains a fractional percentage of carbon dioxide and, if produced by low temperature shift, of carbon monoxide. These gases are rendered harmless preferably by methanation, typically using a supported nickel catalyst at an inlet temperature of 250-350°C.
  • the gas is then cooled and dried and then compressed to synthesis pressure. If desired, it can be compressed before methanation.
  • the conditions of ammonia synthesis can be generally as described in our European puplished application 993.
  • the synthesis catalyst outlet temperature is preferably also low, for example in the range 300-450°C, to obtain a more favourable equilibrium.
  • the catalyst volume is typically 100-200 m 3 per 1000 metric tons per day ammonia output, and is chosen preferably to give an ammonia content of 10-15% v/v in reacted synthesis gas.
  • Recovery of ammonia is preferably by condensation using moderate refrigeration, to for example between +2 and -10°C. Separation of the hydrogen-enriched and the menthane/nitro- gen stream from reacted synthesis gas can be by a cryogenic, adsorptive or diffusion method.
  • an ammonia production process comprises
  • the H 2 :N 2 molar ratio is preferably in the range 1.5 to 2.3 in the gas entering the synthesis catalyst in step (e). Whatever its ratio within the defined broad or preferred range, it is maintained preferably within 20% of the ratio in the fresh synthesis gas produced in step (d). By this means the rate of flow of the hydrogen recovery stream and thus the power consumption are limited.
  • the required H 2 :N 2 molar ratio in fresh synthesis gas can be attained without excessive catalyst outlet temperatures provided the steam to carbon ratio in the primary and secondary reforming steps is high enough.
  • a steam ratio of at least 3 especially in the range 4-8 is preferably used.
  • the methane content is preferably in the range 25-35% v/v on a dry basis.
  • the methane content of the gas leaving step (b) is preferably in the range 1.5 to 3% on a dry basis. Such methane contents are substantially higher than have previously been considered suitable for ammonia production.
  • step (b) can be fed with oxygen-enriched air, as in the first aspect of the invention.
  • step (a) the steam/hydrocarbon reaction can take place at an outlet temperature as low as 550-650°C. Consequently a catalyst having adequate low temperature activity should be chosen.
  • a very suitable catalyst comprises nickel on a refractory secondary support on a metal or alloy primary support, or on a highly calcined ceramic support, as referenced above.
  • the steps of converting carbon monoxide catalytically with steam and removing carbon oxides can be conventional as described above in relation to the first aspect of the invention. Especially since it is preferred to operate the primary and secondary reforming steps at relatively low temperatures, resulting in a rather higher methane content than was previously considered suitable for ammonia synthesis gas, it is preferred to remove carbon monoxide finally by selective oxidation. This leaves carbon dioxide in the gas, and this can be removed largely by contact with the liquid adsorbent, as disclosed in our European application 993. Residual carbon dioxide can then be removed by methanation or adsorption or treatment with non-regenerable alkali.
  • the conventional sequence of high temperature and low temperature shift can be used, or a single shift stage as described above.
  • the inlet steam-to-gas volume ratio can be at least 0.8 which, with suitable temperature control, enables the outlet CO content to be low enough (up to 0.5% v/v on a dry basis) for final removal by methanation.
  • the CO content can be up to 2.0% v/v whereafter it is removed by selective oxidation, as described above.
  • the conditions of ammonia synthesis can be generally as in the process of the first aspect.
  • a hydrocarbon feedstock natural gas
  • a hydrocarbon feedstock natural gas
  • known means not shown
  • the resulting water-saturated gas is mixed, if necessary, with steam at 16.
  • towers 12 and 39 are not used and all the steam is added as such at 16).
  • the mixture is preheated to 640°C in furnace 18 fired at 20 with natural gas which, for this purpose, need not be thoroughly, if at all, desulphurised.
  • the heated gas is then passed over a supported nickel catalyst in insulated reactor 22.
  • the endothermic methane/steam reaction takes place and the temperature falls, reaching 523°C at the catalyst outlet.
  • the resulting gas is then reheated to 700°C in furnace 24 and passed into secondary reformer 30.
  • a steam of hot oxygen enriched air (32% v/v O2, 600°C) derived from air separation plant 27 in which a feed of compressed air 26 is resolved into a substantially pure nitrogen stream sent to storage 28 and an enriched air stream which is compressed at 31 and further heated at 32.
  • nitrogen stream 29 will be referred to below.
  • secondary reformer 30 the temperature rises initially as hydrogen burns with a flame, but over the catalyst further methane/steam reaction takes place and the temperature falls to 924°C at the catalyst bed outlet.
  • Furnaces 18 and 24 can include flue gas heat recoveries such as expansion turbines, combustion air preheaters and boiler feed water heaters but for the sake of clarity these are not shown.
  • Gas leaving secondary reformer 30 is cooled at 34, which represents heat recovery by higher pressure steam generation and one or more of boiler feed water heating and natural gas preheating.
  • the cooled gas now at about 370°C, is passed into high temperature shift reactor 35 and there it reacts exothermally over an iron chrome catalyst. It is then cooled in heat exchange 36, which usually includes a high pressure boiler and feed water heater, then passed into low temperature shift reactor 37, in which it contacts a copper containing catalyst and its carbon monoxide is almost completely reacted.
  • the shifted gas is cooled with low grade heat recovery at 38 and contacted with water in packed tower 39, in which it becomes cooled and depleted of part of its content of steam.
  • the resulting heated water is passed at 14 in to tower 12 already mentioned.
  • the cool water fed to tower 39 at 40 is derived in part from tower 12 in which heated water from the bottom of tower 39 is cooled by evaporation and partly from supplementary water fed in at 42 from external supplies or from point 50 or 58 to be described.
  • Water-depleted gas leaving tower 39 overhead is passed to cooling, water removal and C0 2 removal units, which are conventional and are indicated generally by item 48.
  • the water contains dissolved carbon dioxide but with simple purification can be fed to point 42.
  • the carbon dioxide can be expanded in an engine to recover energy.
  • the gas contains residual CO and CO 2 , and these are made harmless by preheating the gas and reaction it over a supported nickel catalyst in methanation reactor 54.
  • the gas is then cooled, largely freed of water in catchpot 56 and thoroughly dried in regenerable adsorption unit 60. Water taken at 58 from catchpot 56 can be used at point 42.
  • the dried gas is compressed at 62, mixed at 64 with recycle gas to be described, heated to synthesis inlet temperature and fed to reactor 66 (this reactor is shown with a single catalyst bed but in practice would include a plurality of beds and conventional means for feed gas preheating and temperature control. It is, however, preferred in any event to have feed gas preheater 67 upstream of part of the catalyst, so that hot gas from the downstream-most bed can pass to external heat recovery 68 without cooling). After heat recovery 68 the gas is cooled by conventional means (not shown) including moderate refrigeration, to below the dewpoint to ammonia and passed to catchpot 70 from which liquid product ammonia is run off at 72.
  • Unreacted gas passes out overhead; at this stage it contains less hydrogen per nitrogen molecule than the gas fed to reactor 66, because ammonia formation removes 3 hydrogen molecules per nitrogen molecule, but at 74 it receives a feed of hydrogen-rich gas to be described below.
  • the mixed gas is fed to circulator 76, which increases its pressure by up to 20% and is then divided at 78 into a synthesis recycle stream (which is fed to point 64) and a hydrogen recovery stream. This stream is fed to separation section 80. Here it is washed with water to remove ammonia and dried.
  • Part of the dried gas is taken off at 81 to regenerate absorber 60, th remainder of the gas is resolved cryogenically or by adsorption or selective diffusion into the hydrogen-rich stream 82 fed to point 74 and a waste stream 86, which may have fuel value.
  • the aqueous ammonia is distilled under pressure and the resulting anhydrous ammonia is fed out at 84 to the main product offtake 72.
  • Table 1 sets out the process conditions, gas compositions and hourly flow rates in a process for making 775 metric tons per day of ammonia from a natural gas of average composition CH 3 . 931 containing 2.4% v/v of nitrogen and 0.1% v/v of C0 2 . This process follows the dotted paths on the flowsheet.
  • nitrogen as liquid or compressed gas, accumulates in reservoir 28. Should the plant have to be shut down, this nitrogen (after evaporation if it is in liquid form) is piped by lines (indicated by 29 generally) to the inlets of catalytic reactors. Such nitrogen can be cold or, if a short shut down period is expected, can be preheated to catalyst operating temperature. Nitrogen flow is maintained until process gases have been displaced. If the plant is to be restarted from cold, nitrogen from 29 is preheated and passed through, whereafter burners 20 are lit and the various reactors are brought up to operating temperature. Such nitrogen flow can be on a once-through or recycle basis depending on the capacity of reservoir 28.
  • natural gas is desulphurised by known means (not shown) and fed at 110 to the lower portion of packed tower 112, in which it rises through a falling stream of hot water fed in at 114from a source to be described.
  • the resulting water-saturated gas is mixed, if necessary, with steam at 116.
  • tower 112 and corresponding desaturator tower 139 are not used and all the steam is added as such at 116).
  • the mixture is prehented in the convective section of furnace 118 fired at 120 with synthesis residual gas 86 and natural gas 111, which for this purpose need not be thoroughly, if at all, desulphurised.
  • the heated gas is then passed over a supported nickel catalyst in heated tubes 122.
  • the endothermic methane/Steam reaction takes place, the temperature reaching 629°C at the catalyst outlet.
  • the resulting gas is passed into secondary reformer 130. Here it encounters a stream of hot air (700°C) fed in at 132.
  • the temperature rises initially as hydrogen burns with a flame, but over the catalyst further methane/steam reaction takes place and the temperature falls to 857°C at the catalyst bed outlet.
  • the temperature and rate of feed of air are chosen so that the gas leaving 130 contains nitrogen in excess of what can react later with hydrogen to produce ammonia.
  • Furnace 118 includes also flue gas heat recoveries such as combustion air preheaters and boiler feed water heaters but for the sake of clarity these are not shown.
  • Gas leaving secondary reformer 130 is cooled at 134, which represents heat recovery by high pressure steam generation and one or more of boiler feed water heating and natural gas preheating.
  • the cooled gas now at about 300°C, is passed into shift reactor 136 and there it reactes exothermally over a copper-containing catalyst and becomes heated to 335°C.
  • the gas is cooled with heat recovery in boiler 137. It is contacted with water in packed tower 139 and there cooled and depleted of part of its cotent of steam.
  • the resulting heated water is passed at 114 into tower 112 already mentioned.
  • the cool water fed to tower 138 at 140 is derived in part from tower 112 in which heated water from the bottom of tower 138 is cooled by evaporation and partly from supplementary water fed in at 142 from external supplies orfrom point 150 or 158 to be described.
  • Water-depleted gas leaving tower 139 overhead is reacted with air fed at 146 over a noble metal catalyst in selective oxidation unit 144.
  • the CO-free gas leaving 144 is passed to cooling, water-removal and CO 2 -removal units, which are conventional and are indicated generally by item 148.
  • the water contains dissolved carbon dioxide but with simple purification can be fed to point 142.
  • Carbon dioxide passed out at 152 can be expanded in an engine to recover energy.
  • the gas contains residual C0 2 , and this is made harmless by preheating the gas and reacting it over a supported nickel catalyst in methanation reactor 154.
  • the gas is then cooled, largely freed of water in catchpot 156, thoroughly dried by adsorption in unit 160 and fed to compressor 162. Water taken at 158 from catchpot 156 can be used at point 142.
  • ammonia synthesis section flowsheet items 64 to 86, is the same as in Figure 1.
  • Stream 86 is substantially larger than in the process in Figure 1 and is fed to the burners of furnace 118 as a significant part of its fuel supply.
  • Table 2 sets out the process conditions, gas compositions and hourly flow rates in a process for making 1000 metric tons per day of ammonia from a natural gas of average composition CH 3 . 88 containing 2.4% v/v of nitrogen and 0.1% v/v of C0 2 . This process follows the dotted paths on the flowsheet.
  • the purged residual stream 86 used to fuel furnace 118 contains methane flowing at 146.4 kg mol h- 1 , which is 10% by carbon atoms of the hydrocarbon fed to primary reforming at point 110.

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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EP83301801A 1982-04-14 1983-03-30 Ammonia production process Expired EP0093502B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8210834 1982-04-14
GB8210834 1982-04-14
GB8210835 1982-04-14
GB8210835 1982-04-14

Publications (3)

Publication Number Publication Date
EP0093502A1 EP0093502A1 (en) 1983-11-09
EP0093502B1 EP0093502B1 (en) 1986-05-07
EP0093502B2 true EP0093502B2 (en) 1988-11-17

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EP83301801A Expired EP0093502B2 (en) 1982-04-14 1983-03-30 Ammonia production process

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US (1) US4681745A (OSRAM)
EP (1) EP0093502B2 (OSRAM)
AU (1) AU564149B2 (OSRAM)
CA (1) CA1210222A (OSRAM)
DE (1) DE3363367D1 (OSRAM)
IN (1) IN159188B (OSRAM)

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AU1328183A (en) 1983-10-20
US4681745A (en) 1987-07-21
IN159188B (OSRAM) 1987-04-04
CA1210222A (en) 1986-08-26
DE3363367D1 (en) 1986-06-12
AU564149B2 (en) 1987-08-06
EP0093502B1 (en) 1986-05-07

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